EP0931179B1 - Method for phosphating a steel band - Google Patents
Method for phosphating a steel band Download PDFInfo
- Publication number
- EP0931179B1 EP0931179B1 EP97942941A EP97942941A EP0931179B1 EP 0931179 B1 EP0931179 B1 EP 0931179B1 EP 97942941 A EP97942941 A EP 97942941A EP 97942941 A EP97942941 A EP 97942941A EP 0931179 B1 EP0931179 B1 EP 0931179B1
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- EP
- European Patent Office
- Prior art keywords
- phosphating
- ions
- galvanized
- free
- phosphating solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
- C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
- C23C22/365—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations containing also zinc and nickel cations
Definitions
- the invention relates to a method for phosphating steel strip or steel strip galvanized on one or both sides or alloy galvanized by a Spray or dip treatment, depending on the belt speed for a period of time in the range of 2 to 15 seconds.
- phosphating metal strips in particular electrolytically galvanized or hot-dip galvanized steel strips are state of the art known.
- WO 91/02829 describes a method for Phosphating of electrolytically and / or hot-dip galvanized steel strip through short-term treatment with acid phosphating solutions, which in addition to zinc and phosphate ions, manganese and nickel cations and anions containing more oxygen Contain acids with accelerator effect. Under the latter term are especially to understand nitrate ions.
- DE-A-35 37 108 also describes a process for the phosphating of electrolytically galvanized steel strips Treatment with acid phosphating solutions, which in addition to zinc, manganese and Phosphate ions other metal cations such as nickel ions and / or Anions of oxygen-containing acids with accelerating action, in particular Nitrate ions included.
- acid phosphating solutions which in addition to zinc, manganese and Phosphate ions other metal cations such as nickel ions and / or Anions of oxygen-containing acids with accelerating action, in particular Nitrate ions included.
- the content of zinc cations lies in that relatively deep range from 0.1 to 0.8 g / l.
- DE-A-42 28 470 teaches Process for the phosphating of one-sided electrolytically galvanized steel strip the galvanized surface by treatment with acid phosphating solutions, the 1.0 to 6.0 g / l zinc cations, 0.5 to 5.0 g / l nickel cations and 14 to 25 g / l Contain phosphate anions.
- acid phosphating solutions the 1.0 to 6.0 g / l zinc cations, 0.5 to 5.0 g / l nickel cations and 14 to 25 g / l Contain phosphate anions.
- water-soluble Salts of the cations mentioned for example the nitrates, can be used.
- the cations mentioned would be used in the form of their nitrates, the nitrate content would have no influence on the phosphating result.
- the phosphating processes known in the prior art form phosphate layers with a mass per unit area of up to approximately 2.0 g / m 2 on the galvanized surface of steel strips galvanized on one or both sides.
- galvanized steel surfaces could not be phosphated due to the short phosphating times in the range of about 2 to about 15 seconds.
- no phosphate layer was formed on the non-galvanized side. This could have been desirable. If these single-sided galvanized and phosphated steel strips were later installed as parts of automobile bodies and phosphated again, the phosphating of the steel side often proved to be problematic because of the passivation caused by the pretreatment.
- WO-A-95/07370 discloses a method for phosphating metal surfaces made of steel, galvanized or alloy galvanized steel, aluminum, aluminized or alloy-aluminized steel, in particular for the treatment of single or steel galvanized on both sides.
- the metal surfaces in contact with a phosphating solution that is free of nickel, Cobalt, copper, nitrite and oxo anions of halogens and which is 0.3 to 2 g / l Zn (II), 0.3 to 4 g / l Mn (II), 5 to 40 g / l phosphate ions, 0.1 to 5 g / l hydroxylamine in free or bound form and / or 0.2 to 2 g / l m-nitrobenzenesulfonate and contains at most 0.5 g / l nitrate ions, the Mn content at least 50% of Zn content is.
- a phosphating solution that is free of nickel, Cobalt, copper, nitrite and oxo anions of halogens and which is 0.3 to 2 g / l Zn (II), 0.3 to 4 g / l Mn (II), 5 to 40 g / l phosphate ions,
- the total acidity value should be between 15 and 25 points and the value of the free acid at band phosphating between 0.3 and 2.5 Points.
- the process is for use in dipping, spraying or Spray / immersion process suitable.
- the band phosphating in the steel mill treatment times between 5 and 12 seconds; the appropriate bath temperatures between 30 and 70 ° C.
- the invention has for its object a phosphating process for high-speed To provide conveyor systems through which not only the galvanized side of galvanized or alloy galvanized steel strip can be phosphated, but also non-galvanized steel strips or the non-galvanized side from one side galvanized steel strips.
- This provides a material that advantageously for the construction of, for example, vehicle bodies or Household appliances such as refrigerators and washing machines can be used.
- This object is achieved by a method for phosphating steel strip or steel strip galvanized on one or both sides or galvanized with alloys by spraying or dipping treatment for a period in the range from 2 to 15 seconds with an acidic, zinc and manganese-containing phosphating solution with a temperature in the range from 40 to 70 ° C, the phosphating solution 1 to 4 g / l Zinc ions, 0.8 to 3.5 g / l Manganese ions 10 to 30 g / l Phosphate ions 0.1 to 3 g / l Hydroxylamine in free, ionic or bound form and contains no more than 1 g / l nitrate ion, has a free acid content in the range from 0.4 to 4 points and a total acid content in the range from 12 to 50 points, characterized in that the phosphating solution contains at least one further cation selected from nickel ions in amounts of 0.8 to 3.5 g / l or copper ions in amounts of 0.002 to
- the steel strips can be galvanized or hot-dip galvanized or be galvanized.
- "Galvanized alloy” means that the Steel surface was coated with an alloy that other than zinc Contains metals such as iron, nickel or aluminum.
- a Alloy galvanizing with a zinc-iron alloy can, for example, thereby take place that one anneals a galvanized steel strip, whereby a diffusion of Iron atoms in the zinc layer and vice versa.
- the layer thicknesses of the Galvanizing layers are usually in the range from about 5 to about 20 ⁇ m.
- free acid and total acid are in the field of Commonly known phosphating. They are determined by looking at the acidic one Titrate the bath sample with 0.1 normal sodium hydroxide solution and measure its consumption. The Consumption in ml is given as a score. In this document, under the Score of free acid consumption in ml of 0.1 normal sodium hydroxide solution understood to 10 ml bath solution, diluted to 50 ml with deionized water was titrated to pH 3.6. Similarly, the score gives the Total acid consumption in ml up to a pH of 8.2.
- hydroxylamine or its compounds in low-nitrate or nitrate-free phosphating solutions for high-speed It is now possible for the first time to also use galvanized steel surfaces with spray or dipping processes. For those with longer treatment times Working part phosphating is the use of hydroxylamine as In contrast, accelerators have long been known. Examples of this are EP-A-315 059 and WO 93/03198. Hydroxylamine can be used as a free base, as Hydroxylamine-releasing compound such as hydroxylamine complexes as well as ketoximes or aldoximes or in the form of hydroxylammonium salts be used.
- the total phosphorus content of the phosphating bath is considered to be present in the form of phosphate ions PO 4 3- . Accordingly, the known fact that the pH values of the phosphating baths in the range from about 2.0 to about 3.6, which are in the acidic region, only a very small part of the phosphate is actually in the form is ignored in the concentration calculation or determination the triple negatively charged anions are present. At these pH values it is rather to be expected that the phosphate is present primarily as a single negatively charged dihydrogen phosphate anion, together with undisociated phosphoric acid and with smaller amounts of double negatively charged hydrogen phosphate anions.
- phosphating solutions that range from 0.002 to 0.2 g / l copper ions, in particular about 0.003 to about 0.06 g / l copper ions contain.
- the phosphating solutions contain Alkali metal and / or ammonium cations to determine the value of the free acid on the set the desired range.
- the presence of Fluoride ions are generally not required in the phosphating solution.
- the Phosphating of hot-dip galvanized steel strips is caused by fluoride ions however easier and also for the phosphating of electrolytically galvanized Steel strip can ensure the presence of fluoride ions for even Layer training can be advantageous.
- the preferred fluoride contents in the range of 0.0 to about 0.5 g / l, in particular in the range from about 0.1 to about 0.2 g / l.
- the phosphating solutions are generally prepared in the Known to those skilled in the art.
- phosphate is in the form of Phosphoric acid introduced into the phosphating solutions.
- the cations are in Form of acid-soluble compounds such as carbonates, oxides or the hydroxides of phosphoric acid are added so that they are partially neutralized becomes. Further neutralization to the desired pH range takes place preferably by adding sodium hydroxide or sodium carbonate.
- the Optional copper ions can preferably also be used as sulfate or as Acetate are introduced into the phosphating solution.
- As a source more free Fluoride anions are suitable, for example, sodium or potassium fluoride.
- Complex fluorides can be, for example, tetrafluoroborate or hexafluorosilicate be used.
- the invention relates to the use of the phosphating process described above for the production on both sides of phosphate layers with a mass per unit area in the range from 0.4 to 2.0 g / m 2 on steel strip or on steel strip galvanized or alloy-galvanized on one or both sides.
- Phosphate layers with a mass per unit area in the range from approximately 0.9 to approximately 1.8 g / m 2 are preferably produced.
- the mass per unit area can, as is known to the person skilled in the art, be determined by weighing a phosphated sample sheet, detaching the phosphate layer in 5% chromic acid solution and weighing the sample sheet back. This method is described, for example, in DIN 50942.
- phosphating solutions whose free acid content is in the range from about 1.5 to about 2.5 points and total acid in the range of about 20 to about 35 points.
- the temperature of the treatment solution is preferably in the range from approximately 50 to 70 ° C. and in particular in the range from approximately 55 to approximately 65 ° C.
- Preferred treatment times range from about 5 to about 10 seconds.
- the metal surface Before applying the phosphating solution, the metal surface be completely water wettable. This is in continuous working Belt systems are usually given. If the belt surface is oiled this oil should be cleaned with a suitable cleaner before phosphating remove. The procedures for this are common in the art.
- activating agents Usually solutions or Suspensions used that contain titanium phosphates and sodium phosphates.
- Phosphating process which is advantageously a passivating rinse follows. This takes place between phosphating and passivating rinsing usually an intermediate rinse with water. For a passivating Rinsing treatment baths containing chromic acid are widespread.
- the metal tapes phosphated according to the invention can be used directly with a organic coating. However, you can also start with unpainted condition after cutting, shaping and joining to components like Automobile bodies or household appliances are put together. The hereby associated forming processes are facilitated by the phosphate layer. Is the Corrosive stress on the finished components is low, for example at Household appliances, can be assembled from the pre-phosphated metal Devices can be painted directly. For higher corrosion protection requirements, like them For example, in the automotive industry, it is advantageous, according to Reassembly of the bodies followed by phosphating treatment to let.
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Abstract
Description
Die Erfindung betrifft ein Verfahren zum Phosphatieren von Stahlband oder von ein- oder beidseitig verzinktem oder legierungsverzinktem Stahlband durch eine Spritz- oder Tauchbehandlung, die je nach Bandgeschwindigkeit für eine Zeitdauer im Bereich von 2 bis 15 Sekunden erfolgt.The invention relates to a method for phosphating steel strip or steel strip galvanized on one or both sides or alloy galvanized by a Spray or dip treatment, depending on the belt speed for a period of time in the range of 2 to 15 seconds.
Verfahren zum Phosphatieren von Oberflächen aus Eisen, Stahl, Zink und dessen Legierungen sowie Aluminium und dessen Legierungen sind seit langem Stand der Technik. Das Phosphatieren der genannten Oberflächen dient zur Erhöhung der Haftfestigkeit von Lackschichten und zur Verbesserung des Korrosionsschutzes. Die Phosphatierung erfolgt durch Eintauchen der Metalloberflächen in die Phosphatierlösungen oder durch Bespritzen der Metalloberflächen mit den Phosphatierunglösungen. Kombinierte Verfahren sind ebenfalls bekannt. Phosphatiert werden können geformte Metallteile wie beispielsweise Automobilkarossen, aber auch Metallbänder in schnellaufenden Bandanlagen. Die vorliegende Erfindung befaßt sich mit einer derartigen Bandphosphatierung. Bandphosphatierung unterscheidet sich von Teilephosphatierung dadurch, daß aufgrund der hohen Bandgeschwindigkeiten die Phosphatierung, d. h. das Aufwachsen einer geschlossenen Metallphosphatschicht, innerhalb einer kurzen Zeitspanne von beispielsweise etwa 2 bis etwa 15 Sekunden erfolgen muß.Process for phosphating surfaces made of iron, steel, zinc and the like Alloys as well as aluminum and its alloys have long been the Technology. The phosphating of the surfaces mentioned serves to increase the Adhesive strength of lacquer layers and to improve corrosion protection. The phosphating takes place by immersing the metal surfaces in the Phosphating solutions or by spraying the metal surfaces with the Phosphating solutions. Combined methods are also known. Shaped metal parts such as, for example, can be phosphated Automotive bodies, but also metal strips in high-speed conveyor systems. The The present invention is concerned with such a band phosphating. Band phosphating differs from partial phosphating in that due to the high belt speeds, the phosphating, d. H. the Growing a closed metal phosphate layer within a short Period of time from about 2 to about 15 seconds, for example.
Verfahren zur Phosphatierung von Metallbändern, insbesondere von elektrolytisch verzinkten oder schmelztauchverzinkten Stahlbändern, sind im Stand der Technik bekannt. Beispielsweise beschreibt die WO 91/02829 ein Verfahren zur Phosphatierung von elektrolytisch und/oder schmelztauchverzinktem Stahlband durch kurzzeitige Behandlung mit sauren Phosphatierungslösungen, die neben Zink- und Phosphationen Mangan- und Nickelkationen sowie Anionen sauerstoffhaltiger Säuren mit Beschleunigerwirkung enthalten. Unter letzterem Begriff sind insbesondere Nitrationen zu verstehen. Die DE-A-35 37 108 beschreibt ebenfalls ein Verfahren zur Phosphatierung von elektrolytisch verzinkten Stahlbändern durch Behandlung mit sauren Phosphatierungslösungen, die neben Zink-, Mangan- und Phosphationen weitere Metallkationen wie beispielsweise Nickelionen und/oder Anionen sauerstoffhaltiger Säuren mit Beschleunigerwirkung, insbesondere Nitrationen, enthalten. Die Gehalte an Zink-Kationen liegen dabei in dem verhältnismäßig tiefen Bereich von 0,1 bis 0,8 g/l. Die DE-A-42 28 470 lehrt ein Verfahren zur Phosphatierung von einseitig elektrolytisch verzinktem Stahlband auf der verzinkten Fläche durch eine Behandlung mit sauren Phosphatierungslösungen, die 1,0 bis 6,0 g/l Zink-Kationen, 0,5 bis 5,0 g/l Nickel-Kationen und 14 bis 25 g/l Phosphat-Anionen enthalten. In der Beschreibung hierzu wird festgestellt, daß als Ausgangsprodukte zur Herstellung der Phosphatierungslösungen wasserlösliche Salze der genannten Kationen, beispielsweise die Nitrate, eingesetzt werden können. Im allgemeinen würden die genannten Kationen in Form ihrer Nitrate eingesetzt, wobei der Nitratgehalt keinen Einfluß auf das Phosphatierergebnis hätte.Process for phosphating metal strips, in particular electrolytically galvanized or hot-dip galvanized steel strips are state of the art known. For example, WO 91/02829 describes a method for Phosphating of electrolytically and / or hot-dip galvanized steel strip through short-term treatment with acid phosphating solutions, which in addition to zinc and phosphate ions, manganese and nickel cations and anions containing more oxygen Contain acids with accelerator effect. Under the latter term are especially to understand nitrate ions. DE-A-35 37 108 also describes a process for the phosphating of electrolytically galvanized steel strips Treatment with acid phosphating solutions, which in addition to zinc, manganese and Phosphate ions other metal cations such as nickel ions and / or Anions of oxygen-containing acids with accelerating action, in particular Nitrate ions included. The content of zinc cations lies in that relatively deep range from 0.1 to 0.8 g / l. DE-A-42 28 470 teaches Process for the phosphating of one-sided electrolytically galvanized steel strip the galvanized surface by treatment with acid phosphating solutions, the 1.0 to 6.0 g / l zinc cations, 0.5 to 5.0 g / l nickel cations and 14 to 25 g / l Contain phosphate anions. In the description of this it is stated that as Starting products for the preparation of the phosphating solutions water-soluble Salts of the cations mentioned, for example the nitrates, can be used. In general, the cations mentioned would be used in the form of their nitrates, the nitrate content would have no influence on the phosphating result.
Durch die im Stand der Technik bekannten Phosphatierverfahren werden auf der verzinkten Oberfläche von ein- oder beidseitig verzinkten Stahlbändern Phosphatschichten mit einer flächenbezogenen Masse bis zu etwa 2,0 g/m2 ausgebildet. Unverzinkte Stahloberflächen waren bisher bei den kurzen Phosphatierzeiten im Bereich von etwa 2 bis etwa 15 Sekunden nicht phosphatierbar. Bei der Verwendung von einseitig verzinkten Bändern wurde auf der unverzinkten Seite keine Phosphatschicht ausgebildet. Dies konnte durchaus erwünscht sein. Wurden diese einseitig verzinkten und phosphatierten Stahlbänder später als Teile von Automobilkarossen eingebaut und nochmals phosphatiert, erwies sich die Phosphatierung der Stahlseite wegen einer durch die Vorbehandlung bewirkten Passivierung oft als problematisch.The phosphating processes known in the prior art form phosphate layers with a mass per unit area of up to approximately 2.0 g / m 2 on the galvanized surface of steel strips galvanized on one or both sides. Until now, galvanized steel surfaces could not be phosphated due to the short phosphating times in the range of about 2 to about 15 seconds. When using strips galvanized on one side, no phosphate layer was formed on the non-galvanized side. This could have been desirable. If these single-sided galvanized and phosphated steel strips were later installed as parts of automobile bodies and phosphated again, the phosphating of the steel side often proved to be problematic because of the passivation caused by the pretreatment.
Die WO-A-95/07370 offenbart ein Verfahren zur Phosphatierung von Metalloberflächen aus Stahl, verzinktem oder legierungsverzinktem Stahl, Aluminium, aluminiertem oder legierungsaluminiertem Stahl, insbesondere zur Behandlung von ein-oder beidseitig elektrolytisch verzinktem Stahl. Hierbei werden die Metalloberflächen mit einer Phosphatierlösung in Berührung gebracht, die frei von Nickel, Kobalt, Kupfer, Nitrit und Oxo-Anionen von Halogenen ist und die 0,3 bis 2 g/l Zn(II), 0,3 bis 4 g/l Mn(II), 5 bis 40 g/l Phosphationen, 0,1 bis 5 g/l Hydroxylamin in freier oder gebundener Form und/oder 0,2 bis 2 g/l m-Nitrobenzolsulfonat und höchstens 0,5 g/l Nitrationen enthält, wobei der Mn-Gehalt mindestens 50 % des Zn-Gehalts beträgt. Der Wert der Gesamtsäure soll zwischen 15 und 25 Punkten und der Wert der freien Säure bei Bandphosphatierung zwischen 0,3 und 2,5 Punkten betragen. Das Verfahren ist für die Anwendung im Tauch-, Spritz- oder Spritz/Tauchverfahren geeignet. Bei der Bandphosphatierung im Stahlwerk liegen die Behandlungszeiten zwischen 5 und 12 Sekunden; die geeigneten Badtemperaturen zwischen 30 und 70 °C. WO-A-95/07370 discloses a method for phosphating metal surfaces made of steel, galvanized or alloy galvanized steel, aluminum, aluminized or alloy-aluminized steel, in particular for the treatment of single or steel galvanized on both sides. Here, the metal surfaces in contact with a phosphating solution that is free of nickel, Cobalt, copper, nitrite and oxo anions of halogens and which is 0.3 to 2 g / l Zn (II), 0.3 to 4 g / l Mn (II), 5 to 40 g / l phosphate ions, 0.1 to 5 g / l hydroxylamine in free or bound form and / or 0.2 to 2 g / l m-nitrobenzenesulfonate and contains at most 0.5 g / l nitrate ions, the Mn content at least 50% of Zn content is. The total acidity value should be between 15 and 25 points and the value of the free acid at band phosphating between 0.3 and 2.5 Points. The process is for use in dipping, spraying or Spray / immersion process suitable. The band phosphating in the steel mill treatment times between 5 and 12 seconds; the appropriate bath temperatures between 30 and 70 ° C.
Die Erfindung stellt sich die Aufgabe, ein Phosphatierverfahren für schnellaufende Bandanlagen zur Verfügung zu stellen, durch das nicht nur die verzinkte Seite von verzinktem oder legierungsverzinktem Stahlband phosphatiert werden kann, sondern auch unverzinkte Stahlbänder oder die unverzinkte Seite von einseitig verzinkten Stahlbändern. Hierdurch wird ein Material zur Verfügung gestellt, das vorteilhafterweise für den Bau von beispielsweise Fahrzeugkarosserien oder von Haushaltgeräten wie beispielsweise Kühlschränken und Waschmaschinen verwendet werden kann.The invention has for its object a phosphating process for high-speed To provide conveyor systems through which not only the galvanized side of galvanized or alloy galvanized steel strip can be phosphated, but also non-galvanized steel strips or the non-galvanized side from one side galvanized steel strips. This provides a material that advantageously for the construction of, for example, vehicle bodies or Household appliances such as refrigerators and washing machines can be used.
Diese Aufgabe wird gelöst durch ein Verfahren zum Phosphatieren von Stahlband
oder von ein- oder beidseitig verzinktem oder legierungsverzinktem Stahlband
durch Spritz- oder Tauchbehandlung für eine Zeitdauer im Bereich von 2 bis 15
Sekunden mit einer sauren, zink- und manganhaltigen Phosphatierlösung mit einer
Temperatur im Bereich von 40 bis 70 °C, wobei die
Phosphatierlösung
dadurch gekennzeichnet, daß die Phosphatierlösung wenigstens ein weiteres
Kation, ausgewählt aus Nickelionen in Mengen von 0,8 bis 3,5 g/l oder Kupferionen
in Mengen von 0,002 bis 0,2 g/l, enthält.This object is achieved by a method for phosphating steel strip or steel strip galvanized on one or both sides or galvanized with alloys by spraying or dipping treatment for a period in the range from 2 to 15 seconds with an acidic, zinc and manganese-containing phosphating solution with a temperature in the range from 40 to 70 ° C, the phosphating solution
characterized in that the phosphating solution contains at least one further cation selected from nickel ions in amounts of 0.8 to 3.5 g / l or copper ions in amounts of 0.002 to 0.2 g / l.
Dabei können die Stahlbänder elektrolytisch verzinkt oder schmelztauchverzinkt bzw. legierungsverzinkt sein. Unter "legierungsverzinkt" wird verstanden, daß die Stahloberfläche mit einer Legierung überzogen wurde, die neben Zink andere Metalle wie beispielsweise Eisen, Nickel oder Aluminium enthält. Eine Legierungsverzinkung mit einer Zink-Eisen-Legierung kann beispielsweise dadurch erfolgen, daß man ein verzinktes Stahlband tempert, wodurch eine Diffusion von Eisenatomen in die Zinkschicht und umgekehrt erfolgt. Die Schichtdicken der Verzinkungsschichten liegen üblicherweise im Bereich von etwa 5 bis etwa 20 µm.The steel strips can be galvanized or hot-dip galvanized or be galvanized. "Galvanized alloy" means that the Steel surface was coated with an alloy that other than zinc Contains metals such as iron, nickel or aluminum. A Alloy galvanizing with a zinc-iron alloy can, for example, thereby take place that one anneals a galvanized steel strip, whereby a diffusion of Iron atoms in the zinc layer and vice versa. The layer thicknesses of the Galvanizing layers are usually in the range from about 5 to about 20 μm.
Die Begriffe "freie Säure" und "Gesamtsäure" sind auf dem Gebiet der Phosphatierung allgemein bekannt. Sie werden bestimmt, indem man die saure Badprobe mit 0,1-normaler Natronlauge titriert und deren Verbrauch mißt. Der Verbrauch in ml wird als Punktzahl angegeben. In dieser Schrift wird unter der Punktzahl der freien Säure der Verbrauch in ml an 0,1-normaler Natronlauge verstanden, um 10 ml Badlösung, die mit vollentsalztem Wasser auf 50 ml verdünnt wurde, bis zu einem pH-Wert von 3,6 zu titrieren. Analog gibt die Punktzahl der Gesamtsäure den Verbrauch in ml bis zu einem pH-Wert von 8,2 an.The terms "free acid" and "total acid" are in the field of Commonly known phosphating. They are determined by looking at the acidic one Titrate the bath sample with 0.1 normal sodium hydroxide solution and measure its consumption. The Consumption in ml is given as a score. In this document, under the Score of free acid consumption in ml of 0.1 normal sodium hydroxide solution understood to 10 ml bath solution, diluted to 50 ml with deionized water was titrated to pH 3.6. Similarly, the score gives the Total acid consumption in ml up to a pH of 8.2.
Durch die erfindungsgemäße Kombination von sehr geringen Nitratgehalten bzw. der völligen Abwesenheit von Nitrat im Phosphatierbad und der gleichzeitigen Anwesenheit von Hydroxylamin oder Hydroxylamin-abspaltenden Verbindungen wird die erfindungsgemäße Aufgabe gelöst, auch auf unbeschichteten Stahloberflächen eine geschlossene Metallphosphatschicht aufwachsen zu lassen. Besonders bevorzugt sind für die Phosphatierung von verzinkten Stahlbändern Phosphatierlösungen mit einem Nitratgehalt von nicht mehr als 0,1 g/l und insbesondere völlig nitratfreie Phosphatierlösungen, während für die Phosphatierung von unverzinkten Stahlbändern geringe Nitratgehalte von bis zu 1 g/l tolerierbar oder sogar vorteilhaft sein können.The combination of very low nitrate contents or the complete absence of nitrate in the phosphating bath and the simultaneous Presence of hydroxylamine or hydroxylamine-releasing compounds the object of the invention is achieved, even on uncoated Steel surfaces to grow a closed metal phosphate layer. Are particularly preferred for the phosphating of galvanized steel strips Phosphating solutions with a nitrate content of not more than 0.1 g / l and in particular completely nitrate-free phosphating solutions, while for phosphating Low nitrate contents of up to 1 g / l can be tolerated from non-galvanized steel strips or may even be beneficial.
Durch die Verwendung von Hydroxylamin oder dessen Verbindungen in nitratarmen oder nitratfreien Phosphatierungslösungen für schnellaufende Bandanlagen ist es erstmals möglich, auch unverzinkte Stahloberflächen mit Spritz- oder Tauchverfahren zu phosphatieren. Für die mit längeren Behandlungszeiten arbeitende Teilephosphatierung ist die Verwendung von Hydroxylamin als Beschleuniger demgegenüber seit längerem bekannt. Beispiele hierfür sind die EP-A-315 059 und die WO 93/03198. Hydroxylamin kann als freie Base, als Hydroxylamin-abspaltende Verbindung wie beispielsweise Hydroxylaminkomplexe sowie Ketoxime oder Aldoxime oder in Form von Hydroxylammoniumsalzen eingesetzt werden. Fügt man freies Hydroxylamin dem Phosphatierbad oder einem Phosphatierbad-Konzentrat zu, wird es aufgrund des sauren Charakters dieser Lösungen weitgehend als Hydroxylammonium-Kation vorliegen. Bei einer Verwendung als Hydroxylammonium-Salz sind die Sulfate sowie die Phosphate besonders geeignet. Im Falle der Phosphate sind aufgrund der besseren Löslichkeit die sauren Salze bevorzugt. Um einerseits ökonomischen Gesichtspunkten Rechnung zu tragen und andererseits die Phosphatierbäder mit nicht zu viel Sulfationen zu belasten, kann vorteilhafterweise eine Kombination von freiem Hydroxylamin und Hydroxylammoniumsulfat eingesetzt werden. Hydroxylamin oder seine Verbindungen werden der Phosphatierungslösung in solchen Mengen zugesetzt, daß die rechnerische Konzentration des freien Hydroxylamins zwischen 0,1 bis 3 g/l, vorzugsweise zwischen 0,15 und 0,8 g/l liegt.By using hydroxylamine or its compounds in low-nitrate or nitrate-free phosphating solutions for high-speed It is now possible for the first time to also use galvanized steel surfaces with spray or dipping processes. For those with longer treatment times Working part phosphating is the use of hydroxylamine as In contrast, accelerators have long been known. Examples of this are EP-A-315 059 and WO 93/03198. Hydroxylamine can be used as a free base, as Hydroxylamine-releasing compound such as hydroxylamine complexes as well as ketoximes or aldoximes or in the form of hydroxylammonium salts be used. Add free hydroxylamine to the phosphating bath or a Phosphate bath concentrate too, it becomes due to the acidic nature of this Solutions largely exist as a hydroxylammonium cation. At a The sulfates and the phosphates are used as the hydroxylammonium salt particularly suitable. In the case of phosphates are due to the better solubility the acid salts preferred. On the one hand from an economic point of view To take into account and on the other hand the phosphating baths with not too much Stressing sulfate ions can advantageously be a combination of free Hydroxylamine and hydroxylammonium sulfate are used. Hydroxylamine or its compounds are the phosphating solution in such amounts added that the calculated concentration of free hydroxylamine between 0.1 to 3 g / l, preferably between 0.15 and 0.8 g / l.
Für die Angabe der Phosphatkonzentration wird der gesamte Phosphorgehalt des Phosphatierbades als in Form von Phosphationen PO4 3- vorliegend angesehen. Demnach wird bei der Konzentrationsberechnung bzw. -bestimmung die bekannte Tatsache außer Acht gelassen, daß bei den im sauren Gebiet liegenden pH-Werten der Phosphatierbäder im Bereich von etwa 2,0 bis etwa 3,6 nur ein sehr geringer Teil des Phosphats tatsächlich in Form der 3-fach negativ geladenen Anionen vorliegt. Bei diesen pH-Werten ist vielmehr zu erwarten, daß das Phosphat vornehmlich als einfach negativ geladenes Dihydrogenphosphat-Anion vorliegt, zusammen mit undisoziierter Phosphorsäure und mit geringeren Mengen 2-fach negativ geladener Hydrogenphosphat-Anionen. For the indication of the phosphate concentration, the total phosphorus content of the phosphating bath is considered to be present in the form of phosphate ions PO 4 3- . Accordingly, the known fact that the pH values of the phosphating baths in the range from about 2.0 to about 3.6, which are in the acidic region, only a very small part of the phosphate is actually in the form is ignored in the concentration calculation or determination the triple negatively charged anions are present. At these pH values it is rather to be expected that the phosphate is present primarily as a single negatively charged dihydrogen phosphate anion, together with undisociated phosphoric acid and with smaller amounts of double negatively charged hydrogen phosphate anions.
Die Korrosionsschutz- und Lackhaftungseigenschaften der Phosphatschichten lassen sich verbessern, wenn die Phosphatierlösungen weitere Kationen enthalten, die in die Phosphatschichten mit eingebaut werden. Beispielsweise wirkt sich die Anwesenheit von 0,8 bis 3,5 g/l Nickelionen in den erfindungsgemäßen Phosphatierbädern günstig auf die Lackhaftung aus. Anstelle des toxikologisch fragwürdigen Nickels kann mit ähnlicher Wirkung Kupfer eingesetzt werden. Hierfür setzt man Phosphatierlösungen ein, die 0,002 bis 0,2 g/l Kupferionen, insbesondere etwa 0,003 bis etwa 0,06 g/l Kupferionen enthalten.Leave the corrosion protection and paint adhesion properties of the phosphate layers improve if the phosphating solutions contain further cations, which in the phosphate layers are installed. For example, the Presence of 0.8 to 3.5 g / l nickel ions in the inventive Phosphating baths favorably on paint adhesion. Instead of toxicologically questionable nickel can be used with a similar effect copper. For this purpose, phosphating solutions are used that range from 0.002 to 0.2 g / l copper ions, in particular about 0.003 to about 0.06 g / l copper ions contain.
Außer den genannten schichtbildenden Kationen enthalten die Phosphatierlösungen Alkalimetall- und/oder Ammonium-Kationen, um den Wert der freien Säure auf den erwünschten Bereich einzustellen.In addition to the layer-forming cations mentioned, the phosphating solutions contain Alkali metal and / or ammonium cations to determine the value of the free acid on the set the desired range.
Für die Phosphatierung von unverzinktem Stahl ist die Anwesenheit von Fluoridionen in der Phosphatierlösung in der Regel nicht erforderlich. Die Phosphatierung schmelztauchverzinkter Stahlbänder wird durch Fluoridionen jedoch erleichtert und auch für die Phosphatierung von elektrolytisch verzinktem Stahlband kann die Anwesenheit von Fluoridionen für eine gleichmäßige Schichtausbildung vorteilhaft sein. Demnach besteht eine weitere bevorzugte Ausführungsform der Erfindung darin, Phosphatierlösungen einzusetzen, die bis zu 0,8 g/l Fluorid in freier oder komplex gebundener Form enthalten. Beispielsweise liegen für die Phosphatierung von elektrolytisch verzinktem Stahlband die bevorzugten Fluoridgehalte im Bereich von 0,0 bis etwa 0,5 g/l, insbesondere im Bereich von etwa 0,1 bis etwa 0,2 g/l.For the phosphating of non-galvanized steel, the presence of Fluoride ions are generally not required in the phosphating solution. The Phosphating of hot-dip galvanized steel strips is caused by fluoride ions however easier and also for the phosphating of electrolytically galvanized Steel strip can ensure the presence of fluoride ions for even Layer training can be advantageous. Accordingly, there is another preferred one Embodiment of the invention in using phosphating solutions that up to Contain 0.8 g / l fluoride in free or complex bound form. For example, for the phosphating of electrolytically galvanized Steel band the preferred fluoride contents in the range of 0.0 to about 0.5 g / l, in particular in the range from about 0.1 to about 0.2 g / l.
Die Herstellung der Phosphatierungslösungen erfolgt im allgemeinen in der dem Fachmann bekannten Art und Weise. Phosphat wird beispielsweise in Form von Phosphorsäure in die Phosphatierungslösungen eingebracht. Die Kationen werden in Form säurelöslicher Verbindungen wie beispielsweise der Carbonate, der Oxide oder der Hydroxide der Phosphorsäure zugesetzt, so daß diese teilweise neutralisiert wird. Die weitere Neutralisation auf den erwünschten pH-Bereich erfolgt vorzugsweise durch Zugabe von Natriumhydroxid oder Natriumcarbonat. Die fakultativ einzusetzenden Kupferionen können bevorzugt auch als Sulfat oder als Acetat in die Phosphatierlösung eingebracht werden. Als Quelle freier Fluoridanionen eignen sich beispielsweise Natrium- oder Kaliumfluorid. Als komplexe Fluoride können beispielsweise Tetrafluoroborat oder Hexafluorosilicat eingesetzt werden.The phosphating solutions are generally prepared in the Known to those skilled in the art. For example, phosphate is in the form of Phosphoric acid introduced into the phosphating solutions. The cations are in Form of acid-soluble compounds such as carbonates, oxides or the hydroxides of phosphoric acid are added so that they are partially neutralized becomes. Further neutralization to the desired pH range takes place preferably by adding sodium hydroxide or sodium carbonate. The Optional copper ions can preferably also be used as sulfate or as Acetate are introduced into the phosphating solution. As a source more free Fluoride anions are suitable, for example, sodium or potassium fluoride. As Complex fluorides can be, for example, tetrafluoroborate or hexafluorosilicate be used.
In einem weiteren Aspekt betrifft die Erfindung die Verwendung des vorstehend beschriebenen Phosphatierverfahrens zur beidseitigen Erzeugung von Phosphatschichten mit einer flächenbezogenen Masse im Bereich von 0,4 bis 2,0 g/m2 auf Stahlband oder auf ein- oder beidseitig verzinktem oder legierungsverzinktem Stahlband. Vorzugsweise werden Phosphatschichten mit einer flächenbezogenen Masse im Bereich von etwa 0,9 bis etwa 1,8 g/m2 erzeugt. Die flächenbezogene Masse ("Schichtgewicht") kann, wie dem Fachmann bekannt, durch Wägen eines phosphatierten Probeblechs, Ablösen der Phosphatschicht in 5 %iger Chromsäurelösung und Rückwägen des Probeblechs bestimmt werden. Diese Methode ist beispielsweise beschrieben in DIN 50942. Für die Erzeugung von Phosphatschichten mit der erwünschten flächenbezogenen Masse setzt man bevorzugt Phosphatierlösungen ein, deren Gehalt an freier Säure im Bereich von etwa 1,5 bis etwa 2,5 Punkten und an Gesamtsäure im Bereich von etwa 20 bis etwa 35 Punkten liegt. Die Temperatur der Behandlungslösung liegt vorzugsweise im Bereich von etwa 50 bis 70 °C und insbesondere im Bereich von etwa 55 bis etwa 65 °C. Bevorzugte Behandlungszeiten liegen im Bereich von etwa 5 bis etwa 10 Sekunden. In a further aspect, the invention relates to the use of the phosphating process described above for the production on both sides of phosphate layers with a mass per unit area in the range from 0.4 to 2.0 g / m 2 on steel strip or on steel strip galvanized or alloy-galvanized on one or both sides. Phosphate layers with a mass per unit area in the range from approximately 0.9 to approximately 1.8 g / m 2 are preferably produced. The mass per unit area ("layer weight") can, as is known to the person skilled in the art, be determined by weighing a phosphated sample sheet, detaching the phosphate layer in 5% chromic acid solution and weighing the sample sheet back. This method is described, for example, in DIN 50942. For the production of phosphate layers with the desired area-related mass, preference is given to using phosphating solutions whose free acid content is in the range from about 1.5 to about 2.5 points and total acid in the range of about 20 to about 35 points. The temperature of the treatment solution is preferably in the range from approximately 50 to 70 ° C. and in particular in the range from approximately 55 to approximately 65 ° C. Preferred treatment times range from about 5 to about 10 seconds.
Vor dem Aufbringen der Phosphatierungslösung muß die Metalloberfläche vollständig wasserbenetzbar sein. Dies ist in kontinuierlich arbeitenden Bandanlagen in der Regel gegeben. Falls die Bandoberfläche jedoch beölt sein sollte, ist dieses Öl vor der Phosphatierung durch einen geeigneten Reiniger zu entfernen. Die Verfahren hierfür sind in der Technik geläufig. Vor der Phosphatierung erfolgt üblicherweise eine Aktivierung mit im Stand der Technik bekannten Aktivierungsmitteln. Üblicherweise werden Lösungen bzw. Suspensionen eingesetzt, die Titanphosphate und Natriumphosphate enthalten. Auf die Aktivierung folgt die Anwendung des erfindungsgemäßen Phosphatierverfahrens, dem man vorteilhafterweise eine passivierende Nachspülung folgen läßt. Dabei erfolgt zwischen Phosphatierung und passivierender Nachspülung üblicherweise eine Zwischenspülung mit Wasser. Für eine passivierende Nachspülung sind chromsäurehaltige Behandlungsbäder weit verbreitet. Aus Gründen des Arbeits- und Umweltschutzes sowie aus Entsorgungsgründen besteht jedoch die Tendenz, diese chromhaltigen Passivierbäder durch chromfreie Behandlungsbäder zu ersetzen. Hierfür sind rein anorganische Badlösungen, insbesondere auf Basis von Hexafluorozirkonaten, oder auch organisch-reaktive Badlösungen, beispielsweise auf Basis von substituierten Poly(vinylphenolen) bekannt. Weiterhin können Nachspüllösungen eingesetzt werden, die 0,001 bis 10 g/l eines oder mehrerer der folgenden Kationen enthalten: Lithiumionen, Kupferionen, Silberionen und/oder Wismutionen.Before applying the phosphating solution, the metal surface be completely water wettable. This is in continuous working Belt systems are usually given. If the belt surface is oiled this oil should be cleaned with a suitable cleaner before phosphating remove. The procedures for this are common in the art. Before the Phosphating is usually carried out with activation in the prior art known activating agents. Usually solutions or Suspensions used that contain titanium phosphates and sodium phosphates. On the activation follows the application of the invention Phosphating process, which is advantageously a passivating rinse follows. This takes place between phosphating and passivating rinsing usually an intermediate rinse with water. For a passivating Rinsing treatment baths containing chromic acid are widespread. Out For reasons of work and environmental protection as well as for disposal reasons however, the tendency to pass these chromium-containing passivation baths through chromium-free ones To replace treatment baths. Purely inorganic bath solutions are in particular based on hexafluorozirconates, or also organically reactive Bath solutions, for example based on substituted poly (vinylphenols) known. Rinse solutions that are 0.001 to 10 can also be used g / l of one or more of the following cations contain: lithium ions, Copper ions, silver ions and / or bismuth ions.
Die erfindungsgemäß phosphatierten Metallbänder können direkt mit einer organischen Beschichtung versehen werden. Sie können jedoch auch im zunächst unlackierten Zustand nach Schneiden, Formen und Fügen zu Bauteilen wie Automobilkarosserien oder Haushaltsgeräten zusammengefügt werden. Die hiermit verbundenen Umformvorgänge werden durch die Phosphatschicht erleichtert. Ist die korrosive Beanspruchung der fertigen Bauteile gering, wie beispielsweise bei Haushaltsgeräten, können die aus dem vorphosphatierten Metall zusammengebauten Geräte direkt lackiert werden. Für höhere Korrosionsschutzanforderungen, wie sie beispielsweise im Automobilbau gestellt werden, ist es vorteilhaft, nach dem Zusammenbau der Korosserien nochmals eine Phosphatierbehandlung folgen zu lassen.The metal tapes phosphated according to the invention can be used directly with a organic coating. However, you can also start with unpainted condition after cutting, shaping and joining to components like Automobile bodies or household appliances are put together. The hereby associated forming processes are facilitated by the phosphate layer. Is the Corrosive stress on the finished components is low, for example at Household appliances, can be assembled from the pre-phosphated metal Devices can be painted directly. For higher corrosion protection requirements, like them For example, in the automotive industry, it is advantageous, according to Reassembly of the bodies followed by phosphating treatment to let.
Die Erfindung wird durch die nachfolgenden Ausführungsbeispiele (Tabelle) näher erläutert. The invention is explained in more detail by the following exemplary embodiments (table).
Claims (5)
- A process for phosphating steel strip or steel strip galvanized or alloy-galvanized on one or both sides by spraying or dipping for between 2 and 15 seconds with or in an acidic zinc- and manganese-containing phosphating solution with a temperature of 40 to 70°C, the phosphating solution containing1 to 4 g/l zinc ions,0.8 to 3.5 g/l manganese ions,10 to 30 g/l phosphate ions,0.1 to 3 g/l hydroxylamine in free, ionic or bound form
- A process as claimed in claim 1, characterized in that the phosphating solution contains up to 0.8 g/l fluoride in free or complexed form.
- A process as claimed in claim 1 or 2, characterized in that the phosphating solution contains up to 1 g/l nitrate ions in the phosphating of non-galvanized steel and no more than 0.1 g/l nitrate ions in the phosphating of galvanized steel.
- A process as claimed in one or more of claims 1 to 3, characterized in that the phosphating solution contains 0.15 to 0.8 g/l hydroxylamine in free, ionic or bound form.
- The use of the process claimed in one or more of claims 1 to 4 for the formation of phosphate layers with a weight per unit area of 0.4 to 2.0 g/m2 on both sides of steel strip or on both sides of steel strip galvanized or alloy-galvanized on one or both sides.
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DE19639596A DE19639596A1 (en) | 1996-09-26 | 1996-09-26 | Process for phosphating steel strips |
DE19639596 | 1996-09-26 | ||
PCT/EP1997/005091 WO1998013534A2 (en) | 1996-09-26 | 1997-09-17 | Method for phosphating a steel band |
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JP (1) | JP2001508123A (en) |
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US6179934B1 (en) | 1997-01-24 | 2001-01-30 | Henkel Corporation | Aqueous phosphating composition and process for metal surfaces |
JPH10204649A (en) * | 1997-01-24 | 1998-08-04 | Nippon Parkerizing Co Ltd | Aqueous phosphate treating solution for metallic surface and its treatment |
DE19740953A1 (en) * | 1997-09-17 | 1999-03-18 | Henkel Kgaa | High speed spray or dip phosphating of steel strip |
DE19808755A1 (en) | 1998-03-02 | 1999-09-09 | Henkel Kgaa | Layer weight control for strip phosphating |
DE19905479A1 (en) * | 1999-02-10 | 2000-08-17 | Metallgesellschaft Ag | Process for the phosphatisation of zinc or aluminum surfaces |
DE10110833B4 (en) * | 2001-03-06 | 2005-03-24 | Chemetall Gmbh | Process for applying a phosphate coating and use of the thus phosphated metal parts |
DE10110834B4 (en) * | 2001-03-06 | 2005-03-10 | Chemetall Gmbh | Process for coating metallic surfaces and use of the substrates coated in this way |
CN104313579B (en) * | 2014-11-11 | 2017-01-18 | 武汉钢铁(集团)公司 | Production method of zinc-magnesium galvanized alloy steel plate |
CN105568274A (en) * | 2015-12-31 | 2016-05-11 | 安徽红桥金属制造有限公司 | Environment-friendly galvanizing passivator and preparation method thereof |
CN105925985B (en) * | 2016-07-19 | 2018-04-20 | 东莞市凯盟表面处理技术开发有限公司 | A kind of stainless iron room temperature chemical polishing solution and preparation method thereof and application method |
CN111349867A (en) * | 2020-04-10 | 2020-06-30 | 武汉钢铁有限公司 | Coating-friendly pre-phosphorized electro-galvanized automobile outer plate and preparation method thereof |
CN112226755B (en) * | 2020-09-23 | 2023-06-23 | 山东大业股份有限公司 | Phosphating method and device for metal wire surface treatment |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4228470A1 (en) * | 1992-08-27 | 1994-03-03 | Henkel Kgaa | Process for phosphating steel strips galvanized on one side |
DE4241134A1 (en) * | 1992-12-07 | 1994-06-09 | Henkel Kgaa | Process for phosphating metal surfaces |
ATE162233T1 (en) * | 1993-09-06 | 1998-01-15 | Henkel Kgaa | NICKEL-FREE PHOSPHATING PROCESS |
DE19606018A1 (en) * | 1996-02-19 | 1997-08-21 | Henkel Kgaa | Zinc phosphating with low levels of nickel and / or cobalt |
-
1996
- 1996-09-26 DE DE19639596A patent/DE19639596A1/en not_active Withdrawn
-
1997
- 1997-09-17 CA CA002266625A patent/CA2266625A1/en not_active Abandoned
- 1997-09-17 WO PCT/EP1997/005091 patent/WO1998013534A2/en not_active Application Discontinuation
- 1997-09-17 ID IDW990112A patent/ID21474A/en unknown
- 1997-09-17 AT AT97942941T patent/ATE197969T1/en not_active IP Right Cessation
- 1997-09-17 AU AU44593/97A patent/AU4459397A/en not_active Abandoned
- 1997-09-17 JP JP51522798A patent/JP2001508123A/en active Pending
- 1997-09-17 KR KR1019990702409A patent/KR20000048509A/en not_active Application Discontinuation
- 1997-09-17 EP EP97942941A patent/EP0931179B1/en not_active Expired - Lifetime
- 1997-09-17 CN CN97198236A patent/CN1231706A/en active Pending
- 1997-09-17 ES ES97942941T patent/ES2153217T3/en not_active Expired - Lifetime
- 1997-09-17 DE DE59702741T patent/DE59702741D1/en not_active Expired - Fee Related
Also Published As
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WO1998013534A2 (en) | 1998-04-02 |
DE59702741D1 (en) | 2001-01-11 |
ATE197969T1 (en) | 2000-12-15 |
AU4459397A (en) | 1998-04-17 |
DE19639596A1 (en) | 1998-04-02 |
WO1998013534A3 (en) | 1998-08-27 |
KR20000048509A (en) | 2000-07-25 |
ES2153217T3 (en) | 2001-02-16 |
ID21474A (en) | 1999-06-17 |
EP0931179A2 (en) | 1999-07-28 |
CN1231706A (en) | 1999-10-13 |
JP2001508123A (en) | 2001-06-19 |
CA2266625A1 (en) | 1998-04-02 |
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